Method of treating oil



Dec. E9, 1922.

C. F, KENNEDY. METHOD OF TREATING 0| 2 SHEETS-SHEET l FlLED MAY 24. 1919.

Qu# SQA@ ATTORNEY.

:542mm M525 2 SHEETS-SHEET 2 C. F. KENNEDY METHOD OF TREATlNG 0| L FILED MAY 24. 1919.

Dec. A19, 1922.'

Aria/mfr.

223.95% E2G m @WN Patented Dec. 19, 1922.

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CHARLES F. KENNEDY, 0F PHILADELPHIA, PENNSYLVANIA, ASSIGNOR TO THE ATLANTIC REFINING COMPANY, OF PHILADELPHIA, PENNSYLVANIA, A COR- PORATION OF PENNSYLVANIA.

METHOD OF TREATING OIL.

To all whomt may concern.'

Be it known that l, CHARLES l". KENNEDY, a citizen ofthe United States, residing in the city and county of Philadelphia, State of Pennsylvania, have invented certain new and useful Improvements in Methods of Treating Oil, of which the` followingr is a specification.

My invention relates to the treatment of mineral oils, as petroleum, or improving refinery methods andi for improving the character and yield of products.

My invention resides in a method of washing mineral oils, as petroleum, including petroleum products, paraiine wax and slack waxfor improving odor or color, 'or for rendering the same non-emulsifying, by recourse to a vsuitably ldiluted solution of soap or soaps, comprising the alkali metal or ammonium salts of those organic or sulfonic acids found in or derived from acid sludge resulting from the treatment by strong or fuming sulphuric acid of petroleum or petroleum distillates or products, and more particularly found in acid coke or tar derived from acid sludge.

My invention resides also in the washing with a suitable solution of soap orsoaps comprising alkali metal or ammonium salts of organic acids, including the above men- .A

tioned sludge sulfonates, of wax bearing mineral oil, as petroleum, and particularly waX bearing distillate and stock,- paraine distillate, and paraine slops, prior to chilling and pressing, for improving the crystalline structure of the wax formed upon chilling the oil, with resultant improved pressing qualities ofthe oil, better and more complete separation of the waxupon the filter medium, a resultant improved slack wax, and a resultant improvement in 'the filtered or pressed oil. ,K

My invention resides also in washing crude paraiiine wax or crude scale wax, produced from ordinary slack wax or slack wax resulting from washing of the wax bearing oil prior to chilling and pressing; and my .invention resides'gfurther in such method of treating crude pifaffine wax or crude scale wax in advance of effect improved economy and efficiency of the filtering medium, as fullers earth.

My invention resides also in mixing and then washing, or in washing and then mixing filtration of the same to.

wax bearing cuts or distillates differing as to their'viscosities, whereby the heavier wax bearing cut or distillate may be more directly chilled and -pressed without recourse to intermediate cracking distillation; and more particularly,'where one of said distillates or cuts, as paraline slops, is characterized by the amorphous form or extremely fine subdivision of crystals of paraiine Wax content therein heretofore preventing satisfactory cold pressing of the same.

My invention resides also in improving the pressing qualities of a wax bearing oil by subjecting it to washing of the character above referred to, whereby a` wax bearing oil of Viscosity higher, within limits, than has heretofore been found suitable for chilling and pressing, may readily be chilled and pressed because of the formation of the wax upon chilling into larger crystals.

My invention resides in the washing, prior to cold settling, of wax bearing oil, particularly heavy lubricating stock, as cylinder stock, which,l upon dilution with naphtha or equivalent, and when chilled, allows more rapid and complete settling therefrom of solids of the nature of petrolatum containing amorphous wax.

My invention resides in the methods hereinafter described and claimed.

For an understanding of some of the numerous modes of practicing my invention, reference is to be had to the accompanying drawings, in which:

F ig. 1 is a chart of one of various examples of fractional distillation of petroleum in connection with which my invention may b'e practiced.

Fig. 2 is a chart of one of various ex.- amples of cracking distillation of petroleum in connection with which my invention may be practiced. i

ln washing mineral oils, as petroleum or petroleum products, for removing odor, improving color, rendering an oil non-emulsifying, for improving crystalline structure of paraliine wax, etc., with soap solution for removing from the oil or wax solids in linely divided or colloidal state therein, or other foreign matter, as explained and described in the copending aplication of E. M. Johansen,` Ser. No. 295,496, I have discovered it to be a marked and beneficial improvement to employ as the soap or a substantial part i or thereof the alkali lretal or ammonium salts of'organic, as sulfonic acids, found in or deblack acid soaps,l for any suitable or depension, or other foreign matter.

aci-d sludge.

sirable Washing of an oil, and particularly petroleum or any fraction, cut o1' product thereof, including gasolene, naphtha, lamp pil, ga@ Soil, etc. I

In the hereinafter described methods the washing referred to is also preferably effected by the use of these preferred soaps, though in many of the aspects of my invention it is not limited to the particular character of soap employed.

In Fig. 1 there is indicated in chart formone of various possible modes of procedure for the fractional distillation of crude petroleum, any ofthe fractions or products of which it will be understood may be Washed 'Whenever suitable or desirable, with a solution of my above mentioned preferred soap.

As indicated in Fig. 1, there may be taken separate light and heavy Wax bearing cuts or fractions, which may be of any suitable or desired gravities, for example, respectively 37 and 34 degrees B. .These cuts or fractions may be separately treated as indicated, or they may be mixed or taken as a single fraction or cut and then washed or treated in the lmanner indicated.

In the example illustrated'in Fig. 1, the light wax bearing distillate is washed with a solution of any suitable soap, as alkali metal or ammonium salt of resin acid, fatty acid, naphthenic acid, or sulfonic acid, and preferably my hereinbefore described salt of sulfonic acid derived from or found in The soap is employed in aqueous solution, the quantity of soap and degree of dilution being such as to be insufficient for or prevent emulsificlation of the oil While undergoing washing, but sufficient or suitable for removing from the. oil colloidal solids, finely divided solids in rsllse washing is preferably carried on by agitating the oil and soap solution, as by blowing air therethrough, while atatemperature inducing suitable viscosity of the oil.

The washed Wax bearing distillate, which separates from an aqueous layer after the foregoing treatment, has had the conditions affecting its dissolved parafline wax content so altered that it forms larger crystals when chilled, as to 32 degrees F. or lower, With the result that when the Washed distillate is chilled and pressed, Wax more readily and more completely separates therefrom and remains, as usual, upon the filter medium as so-called slack Wax, a mixture of paraffne wax and oil. By so washing the wax bearing oil amorphous or very finely divided crystallinewax is in effect converted into wax of large or sometimes long needle-shaped crystals. The slack wax, andin fact the parafiine Wax derived from the slack wax, are of markedly improved crystalline structure, and of improved odor and color. a

The slack wax resulting from filter pressing the chilled washed Wax bearing distillate may be treated in either of two Ways as indicated. It may be sweated to procure crude scale wax, which may then be meltedv and again washed by suitable aqueous soap solution of the character above referred to,

but preferably one employing my hereinbe as upon fullers earth or equivalent, yielding parafiine wax.

It will be understood that the washing of the crude scale wax is not essential, and' may be resorted to or not, if the light wax bearing `distillate was Washed. In general, however, and broadly, irrespective of the preceding steps leading to the production of crude scale wax, my invention comprehends washing the same as described, for improvement of its color, and odor, andV for improvement of its crystalline structure if the oil in which it was previously contained has not been washed.

Or the slack Wax may be melted and washed by any of the suitable soap solutionsA referredvto, and particularly one employing my preferred soap above described. rIhe resultingwashed slack wax may then be sweate-d to produce a crude scale Wax, which may then again be similarly washed, when melted, though this washing may readily be omitted ifthe slackv wax is washed. The washed crude scale wax may then be melted and filtered, as upon fullers earth or equivalent, to produce paraffine wax.

The Washing ofl the wax saves fullersl earth or' other filtering material because there is left in the wax. less material of by common methods heretofore employed.

Furtherfore, the slack wax, or the paraffine wax derived therefrom, contains a relantively large quantity of low melting point wax. For example, Where previously paraffine Wax was ordinarily procured melt-ing at approximately 118 or 132 degrees F., my Wax contains notl only such high melting point Wax, but in addition relatively large quantity or large proportion of lower-melting point Wax, such, for example, as melts from 105 to 118 degrees F. Because of the Washin of the Wax bearing oil before chill- 'bearing distillate.

then -chilled and pressed, and yielding slack Wax. Here again the Washing increases the yield and improves the character of the wax remaining upon the filter medium. The

slack Wax may then be treated by any suita- I ble method, as by either of the methods hereinbefore described in connection With the slack Wax resulting from the light Wax bearing distillate, to produce parafline Wax or other products.

In place of subjecting the heavy wax bearing stock to the above' described crackling distillation, it is my preference to avoid such cracking distillation, and this may be accomplished by Washing the heavy vva\v bearing stock by an aqueous soap solution of any of the characters above described. The resultant. Washed heavy stock is then chilled and pressed, yielding a slack wax vvhich may then be treated byeither ot' the methods above described in connection with slack Wax resulting from light Wax bearing distillate. In this instance again the Washing improves the yield and quality of slack Wax remaining u on the filtert-medium, the Washinghaving e jected such conditions as to induce format-ion of Wax of large crystalline structure in lieu of amorphous or finely divided crystalline Wax.

'I` he paraii'ine waxes resulting from either of the above described methods of treating heavy Wax bearing stock have the desirable characteristics of the hereinbefore described parafiine waxes as to odor, color, and more particularly crystalline structure and' meltin points.

l'uitable proportions of the light wax bearing distillate and heavy wax bearing stock may be mixed, forexample, in the proportions 0f 70% of the light Wax bearing distillate to 30% of the heavy Wax bearing stock, and the mixture Washed by suitable aqueous solution of soap as described, and

then-chilled and pressed, so yielding a slack Wax which may then be treated by any suitable method, as any of the methods above described, for the production of paraiiine Wax or other products.

Or, in place of 'separating the light Wax bearing distillate and heavy Wax bearing stock as separate fractions or cuts, they may be taken in combination as a single fraction or cut and then Washed in suitable aqueous solution as above described to produce, upon chilling and pressing, a slack Avvax Which may then be treated by any suitable method, as any of the above described methods, to produce paraiine Wax or other products.

In either of the above described cases, Where the light Wax bearing distillate and heavy Wax bearing stock are in mixture, there may be admixed therewith a suitable quantity of low viscosity oil, as gasoil or any other suitable oil, and preferably an oil Which has been previously subjected to filter press operation or which may be derived from a pressed distillate. Such admixture of lovv viscosity oil reduces the viscosity of the mixture for pressing when chilled.

In general, the admixture of such low viscosity oil may be resorted to in connection with any of the oils or mixtures of oils herein described which are to be chilled and pressed', Whenever it is found suitable or desirable to lower the viscosity.

As Well understood-in the oil refining art, some crude oils are reduced by fractional distillation Which drives off only light or low boiling point oils, as naphtha, yielding a so-called reduced oil. This reduced crude oil may then be acid treated, or it may be washed and then acid treated andQ the resultant sourcil neutralized, or acid treated and then neutralized and Washed. In either case the ,neutralized oil may be fractionally distilled substantially as indicated in Fig. 1, light Wax bearing distillate and heavy Wax bearing stock resulting, which may be separately treated as indicated in Fig. 1, or which may be treated in mixture as above dcscribed.

Furthermore, in fractionally distilling 'crude petroleum as indicated in Fig. 1, as Well as in fractionally distilling the washed or acid treated reduced crude oil last above referred to, therev is a residuum in the still which is heavy lvvax bearingoil, as cylinder stock, that is, stock from -which heavy or socalled cylinder lubricating oil may be produced. This residue or cylinder stock may be Washed by suitable aqueous solution ,of soap as above described and upon reducing its viscosity, by addition of naphtha or other suitablel loW viscosity oil, it is chilled and the containedsolids, of the nature'of petrolatum containing amorphous Wax, more readily settleout.

It will further be understood that any two or more of the washed distillates from the light wax bearing distillate, the 'washed distillate resulting from the cracking distillation of heavy wax bearing stock and thel washed heavy stock fromthe heavy wax bearing stock, may be mixed in any suitable proportions and then chilled and pressed to yield slack wax which may then be treated in any of the 'ways hereinbefore described, or otherwise, for producing paraiiine waxor other products.

Referring to Fig, 2, there is indicated one of various forms of cracking distillation of crude petroleum, resulting in lvarious cuts or products any of which, if suitable or desirable, may be washed by my preferred solution of sludge acid soaps or sludge sulfonates.

As indicated, a wax bearing or parafiine distillate is produced; this may be washed with a solution of any of the soaps described, and the washed paraiiine distillate may then be chilled and pressed to yield a slack wax which may then be treated by any method, as any of the methods described in connection with Fig. l, for producing parati-ine wax or other products.

The cracking distillation yields also paraf- 1 fine slops, an oil of higher viscosity. than the parafne distillate and which it has not heretofore been possible immediately to chill and press to procure slack wax.

These paraiiine slops may be rtreated in either o'f two ways, in general similar or analogous to the modes of treatment ofthe heavy wax bearing stock in the case of fractional distillation. The parailine slops may be subjected to a cracking distillation yielding in addition to coke and wax tailings rerun slops which Vare then washed as hereinbefore described with an aqueous solution of any of the suitable soaps described. The washed re-run slops, generally of sufficiently low viscosity or rendered so by addition of low viscosity oil, may then be chilled and pressed yto yield slack wax Awhich may be vtreated by any suitable method, as any of the methods hereinbefore described, to produce paraiiine Wax or other products.

Or the paraiiine slops containing, as aforesaid, the more viscous oil constituents, may be washed by aqueous solution of soap of any suitable character hereinbefore delscribed. The washed parafiine slops may then be suitably diluted with low viscosity oil to reduce viscosity. chilled and pressed to yield slack Wax, which may be treated by any suitable method, as any of the modes described, to produce paraiiine wax or other products.

. It will further be understood that any two or more ofthe Washed paraine distillates derived from the parafiinedistillate, the washed lre-run slops derived from cracking paraiine slops, and washed paraiiine slops derived ture therewith, Without further dilution, of

substantial quantities of washed re-run slops or Washed parailine slops. I

It will be understood also that the paraiiine distillate and paraiiine slops may be mixed in any suitable proportions and then washed to produce a mixture of Washed paraiiine distillate and parafline slops, which may then be chilled and pressed to produce slack wax which may be treated by any method, as any of the modes herein described, for producing paraffin@ Wax or other products. Or the parafiine distillate and paraifine slops may be separately washed and then mixed in any suitable proportion, chilled and pressed to likeends and purposes above described.

Regarding distillations of the characters of both Figs. l and 2, the avoidance of cracking distillation of heavy wax bearing stock and paraiiine slops is desirable in that the alternative method of treatment, to wit, the described Washing of the heavy Wax bearing stock and paraline slops, ensures that the viscosity, which is reduced if the oil is subjected to cracking distillation, is retained, and this is of importance as to the ultimate yield of higher viscosity oils, as lubricating oils, such as derived from the oils separated from the slack wax in the pressing operation, these oilsbeing indicated in Figs. l and 2 as pressed stock and pressed slop oil.- By recourse to Washing-in place of cracking distillation, the yield of high viscosity oils is i approximatelyhtwice the yield when cracking distillation without washing is employed.

By recourse to the method of treating wax bearing oil as herein described, the viscosity of the oil is at least in some instances increased by the washing before chilling and pressing, and such increase in viscosity is a desirable and valuable improvement in the quality of the oil filtrate.

A further advantage arising from my method of Washinga Wax bearing oil before chilling and pressing lies in the fact that oils of viscosity somewhat higherthan the most viscous oils which could heretofore readily be chilled and pressed may now be chilled and pressed to advantage because of theformation of the larger Wax crystals as hereinbefore described. For example, Where heretofore a wax bearing oil of viscosity of 67 to 69 seconds Saybolt at 10Q` degrees F, has generally been the most viscous oil tha-t could readily be chilled and pressed, in accordance with my invention a Wax bearing oil of 80 to 82 seconds Saybolt at. 100 degrees F. if first Washed as described may readily be chilled and pressed. l

The quality of all the pressed Vor filtrate oils herein described, namely, those from which slack Wax has been separated, is markedly improved in that they have higher viscosity, require less acid when acid treated,

and when acid treated the acid sludges are of higher quality in that they are softer and more readily and completely separated from the sour oils, and the quantities of the sludges formed are less, representing, therefore, less loss by occlusion of oil therein; and less of the oils undergoing acid treatment is lost. Because of the more complete separation' of Wax from the oils due to my Washing treatment, these pressed oils are all of better so'-ca1led cold test and lare better in all respects, particularly as regards those qualities desirable in a lubricating oil.

As indicated in Fig. 1, the pressed distillate resulting from the light Wax bearing distillate is fractionally distilled, yielding lubricating stocks, Which are acid treated, by strong or fuming sulphuric acid, yielding sludge and sour oil, the latter .neutralized to yield lubricating oil. It will be understood that the pressed distillate and pressed stock referred to in connection with Fig. 1 and theA pressed distillate, pressed oil and pressed slop oil referred to in connection with Fig. 2 may undergo similar treatment as to distillation, acid treatment and neutralization to produce lubricating oils.

What I claim is:

l. The method of preparing Wax bearing oil for. separating Wax therefrom, which comprises Washing the oil with a soap solu-4 tion of such concentration as to prevent substantial emulsication thereof and to render the Wax more readily separable from the oil. 2. Thevmethod of preparing Wax bearing oil for separating Wax'therefrom, which consists .in Washing-the same with an aqueous solution of soap of such concentration and under such conditions that the Wax may more readily separate from the oil.

3. The methodof preparing Wax bearing oil for separating Wax therefrom, Which consists in Washing the same with an aqueous solution of sludge sulfonates of such concentration and under such conditions that the Wax may be more readily separated from the Oil.v

4. The method of preparing wax bearing oil for separating Wax therefrom, which consi ts in washing the same with an aqueous solution of an alkali metal or ammonium salt of organic acids'from acid sludge, said solution-having such concentration that the Wax is rendered more readily separable from the oil.

5. The method of procuring Wax from` Wax bearing oil, which consists in Washing the oil With an aqueous solution of soap of' such concentration that the Wax is rendered more readily separable from the oil, separating the washed oil, and chilling and pressing the same.

' 6. The method of treating Wax bearing oil, which consists in subjecting the same to cracking distillation, andA Washing a -Wax bearing distillate with an aqueous solution of soap.

Y. T'he methodof treating Wax bearing oil, which consists in subjecting the same to cracking distillation, Washing a Wax bearing distillate With an aqueous solution of soap, and thereafter chilling and pressing the Washed distillate.

8. The method of treating Wax bearingA l oils differing materially as to their Viscosities, which consists in mixing cuts of different viscosities, Washing the same in mixture with each other with an aqueous solution of soap, and chilling andv pressing the Washed mixture.

9. The method of treating Wax bearing oils differing materially as to their viscosities, which consists in mixing cuts of diii'erent viscosities, Washing said oils With an aqueous solution of soap, mixing the` Washed oils, and chilling and pressing the mixtures.

10. The method of treating heavy Wax bearing oil of the character heretofore requiring treatment by cracking distillation for preparing it for chilling and pressing,

Which consists in Washing the oil With aqueous solution of soap, and chilling and pressing the Washed oil. A

11.'The method of treating `heavy Wax bearing .oil of the character heretofore re' quiring treatment by cracking distillation for preparing it for chilling and pressing, which consists in Washing the oil with aqueous solution of soap, and chilling and pressing the Washed oil in the presence of added oil of 10W viscosity.

` 12. The method of separating parafiine Wax from oil residuum, as cylinder stock, which consists in Washing the oil with aqueous solution of soap, and thereafter chilling and settlingthe same.

13. The method of separating paraiine Wax from oil residuum, as cylinder stock, which consists in Washing the oil with aqueoussolution ofisoap in the presence of oil of low viscosity, and thereafter chilling and settling the same.

14. rPhe method of treating paraiiine Wax, which consists in melting the same, and Washing the melted mass with an aqueous solution of a salt of organic acid from acid sludge.

15. The method of treating slack Wax, Which consists in melting"the same, and Washing the melted ma with an aqueous solution of a salt of organic acid from acidv sludge.

16. The method of treating slack Wax, which consists in sweating the same to produce crude scale Wax, Washing the crude scale Wax With a soapfsolution, and thereafter filtering the Washed crude scale Wax through a Vdecolorizing agent.

17. The method of treating crude scale vsolution of soap, separating Wax from the Washed oilderiving lubricating stock from the Wax-free oil, acid treating the lubricating stock, and neutralizing the resultant sour oil to produce lubricating oil.

20. The method of treating Wax bearing oil, Which consists in Washing the oil With an aqueous soap solution, chilling the Washed oil, separating crude Waxtherefrom,

land Washing said Wax with soap solution.

21. The method of treating Wax bearing 'p oil, which consists in Washing the oil with an aqueous solution of soap, chilling and pressing the Washed oil, Washing the re sulting crude Wax with aqueous soap solution, and filtering the Washed crude Wax. 22. The method of treating mineral oil, as petroleum or petroleum product, which consists in subjecting the same to cracking distillation, and Washing a Wax bearing distillate with an aqueous solution of soap.

In testimony whereof I have hereunto afiiXed my signature this 22d day of May, 1919.

CHARLES F. KENNEDY. 

